Colorant stabilizers

ABSTRACT

The present invention is directed to compositions containing a colorant and at least one porphine. The present invention includes an ink set of one or more inks which have substantially identical light fastness properties. One or more of the inks of the ink set includes a colorant and at least one porphine. The porphine imparts light-stability to the colorant so that the colorant does not fade when exposed to electromagnetic radiation such as sunlight or artificial light. The ink set provides a range of colored inks having similar light-stability.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This patent application is a continuation-in-part patent application of U.S. patent application Ser. No. 08/843,410 filed on Apr. 15, 1997, which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/788,863 filed on Jan. 23, 1997, which is a continuation-in-part of Ser. No. 08/757,222 filed on Nov. 11, 1996, now U.S. Pat. No. 5,782,693, which is a continuation-in-part patent application of U.S. patent application Ser. No. 08/627,693 filed on Mar. 29, 1996, now abandoned, all of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a family of colorant stabilizers. The colorant stabilizers, according to the present invention, are capable of stabilizing a colorant when it is exposed to electromagnetic radiation. The colorant stabilizers enable the production of an ink set wherein each ink of the ink set, regardless of color, possesses substantially similar light fastness properties.

BACKGROUND OF THE INVENTION

A major problem with colorants is that they tend to fade when exposed to electromagnetic radiation such as sunlight or artificial light and the like. It is believed that most of the fading of colorants when exposed to light is due to photodegradation mechanisms. These degradation mechanisms include oxidation or reduction of the colorants depending upon the environmental conditions in which the colorant is placed. Fading of a colorant also depends upon the substrate upon which they reside.

Product analysis of stable photoproducts and intermediates has revealed several important modes of photodecomposition. These include electron ejection from the colorant, reaction with ground-state or excited singlet state oxygen, cleavage of the central carbon-phenyl ring bonds to form amino substituted benzophenones, such as triphenylmethane dyes, reduction to form the colorless leuco dyes and electron or hydrogen atom abstraction to form radical intermediates.

Various factors such as temperature, humidity, gaseous reactants, including O₂, O₃, SO₂, and NO₂, and water soluble, nonvolatile photodegradation products have been shown to influence fading of colorants. The factors that effect colorant fading appear to exhibit a certain amount of interdependence. It is due to this complex behavior that observations for the fading of a particular colorant on a particular substrate cannot be applied to colorants and substrates in general.

Under conditions of constant temperature it has been observed that an increase in the relative humidity of the atmosphere increases the fading of a colorant for a variety of colorant-substrate systems (e.g., McLaren, K., J. Soc. Dyers Colour, 1956, 72, 527). For example, as the relative humidity of the atmosphere increases, a fiber may swell because the moisture content of the fiber increases. This aids diffusion of gaseous reactants through the substrate structure.

The ability of a light source to cause photochemical change in a colorant is also dependent upon the spectral distribution of the light source, in particular the proportion of radiation of wavelengths most effective in causing a change in the colorant and the quantum yield of colorant degradation as a function of wavelength. On the basis of photochemical principles, it would be expected that light of higher energy (short wavelengths) would be more effective at causing fading than light of lower energy (long wavelengths). Studies have revealed that this is not always the case. Over 100 colorants of different classes were studied and found that generally the most unstable were faded more efficiently by visible light while those of higher lightfastness were degraded mainly by ultraviolet light (McLaren, K., J. Soc. Dyers Colour, 1956, 72, 86).

The influence of a substrate on colorant stability can be extremely important. Colorant fading may be retarded or promoted by some chemical group within the substrate. Such a group can be a ground-state species or an excited-state species. The porosity of the substrate is also an important factor in colorant stability. A high porosity can promote fading of a colorant by facilitating penetration of moisture and gaseous reactants into the substrate. A substrate may also act as a protective agent by screening the colorant from light of wavelengths capable of causing degradation.

The purity of the substrate is also an important consideration whenever the photochemistry of dyed technical polymers is considered. For example, technical-grade cotton, viscose rayon, polyethylene, polypropylene, and polyisoprene are known to contain carbonyl group impurities. These impurities absorb light of wavelengths greater than 300 nm, which are present in sunlight, and so, excitation of these impurities may lead to reactive species capable of causing colorant fading (van Beek, H. C. A., Col. Res. Appl., 1983, 8(3), 176).

Therefore, there exists a need for methods and compositions which are capable of stabilizing a wide variety of colorants from the effects of both sunlight and artificial light.

SUMMARY OF THE INVENTION

The present invention addresses the needs described above by providing compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range.

The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with a colorant stabilizer. In one embodiment, the colorant stabilizer comprises one or more porphines that have an extremely short triplet state lifetime. (See e.g., Kubat, et al., Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry 96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following structure: ##STR1## wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO₃ H, ##STR2## COOH, or R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.

Examples of such porphines are Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures: ##STR3## The copper ion can also be substituted with an iron or cobalt ion. Other metal ions can be substituted in the porphine molecule as long as the molecule has a relatively short-lived triplet state.

In a further embodiment of the present invention, the colorant stabilizer comprises at least one porphine in combination with at least one metal or metal salt. Unexpectedly, it has been discovered that the incorporation of a relatively small concentration of metal or metal salt into a porphine-containing composition results in superior colorant stability. Preferred metals or metal salts include, but are not limited to, lanthanides and lanthanide salts. Lanthanide elements include scandium, yttium, lanthanum, cerium praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

In order to improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents. Optionally, a surfactant can be added to the metal/porphine composition to increase the interaction of the metal or metal salt and the porphine. In addition to surfactants, other additives such as TINUVIN® compounds (Ciba-Geigy Corporation) may be incorporated into the colorant composition.

The substrates to which the colorant stabilizers are applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate that would benefit from having a stabilized colorant thereon.

In another embodiment, a colorant stabilizer is present in a polymer coating of a heat transfer product, such as is used for transferring graphic images onto clothing.

Accordingly, each of the embodiments of the present invention provide stabilizing molecules that, when one or more of the stabilizing molecules are associated with a colorant, stabilizes the colorant. Therefore, the stabilizing molecules can be used as an additive to any colorant composition. For example, as certain of the stabilizing molecules are poorly soluble in water, they can be directly added to solvent or oil based (not water based) colorant compositions. Additionally, the stabilizing molecules can be added to other colorant compositions that contain additives enabling the solubilization of the stabilizing molecule therein. Further, the stabilizing molecules can be solubilized in an aqueous solution by attaching the molecule to a large water soluble molecule, such as a cyclodextrin.

The colorant stabilizers are particularly effective in ink jet inks. Use of the colorant stabilizers, as described herein, intensifies the colors and stabilizes the colors when exposed to light. Additionally, the colorant stabilizers are particularly effective in paper such as ink jet paper. Use of the colorant stabilizers in a substrate, as described herein, stabilizes a colorant to which it is applied. Also, colorant stabilizers in a substrate has been found to have the unexpected result of reducing the yellowing of the substrate itself upon exposure to light.

The colorant stabilizers are of particular interest in the formation of ink sets, wherein each ink of the ink set, regardless of color, possesses substantially identical light fastness properties as the other inks in the ink set. The ink set enables the production of multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light.

These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.

DETAILED DESCRIPTION OF THE INVENTION

This application is directed to compositions and methods for stabilizing colorants against radiation including radiation in the visible wavelength range. This application is further directed to ink sets comprising one or more inks, each of which possesses substantially identical light stability upon exposure to radiation, including radiation in the visible wavelength range. The compositions and methods relating to stabilizing a colorant by admixing a stabilizing molecule with a colorant solution will first be addressed below. Subsequently, the compositions and methods relating to stabilizing a colorant by applying the colorant to a treated substrate containing a stabilizing molecule will be discussed.

As used herein, the term "composition" and such variations as "colored composition" are used herein to mean a colorant and one or more colorant stabilizers of the present invention. The composition can optionally include a molecular includant.

As used herein, the term "colorant" is meant to include, without limitation, any material which typically will be an organic material, such as an organic colorant or dye. The term is meant to include a single material or a mixture of two or more materials.

The term "light-stable" is used herein to mean that the colorant, when associated with one of the colorant stabilizing molecules of the present invention, is more stable to electromagnetic radiation, including, but not limited to, sunlight or artificial light, than when the colorant is not associated with such a compound.

The term "molecular includant," as used herein, is intended to mean any substance having a chemical structure which defines at least one cavity. That is, the molecular includant is a cavity-containing structure. As used herein, the term "cavity" is meant to include any opening or space of a size sufficient to accept at least a portion of the colorant.

The term "functionalized molecular includant" is used herein to mean a molecular includant to which one or more molecules of a colorant stabilizer are covalently coupled to each molecule of the molecular includant. The term "degree of substitution" is used herein to refer to the number of these molecules or leaving groups (defined below) which are covalently coupled to each molecule of the molecular includant.

The term "derivatized molecular includant" is used herein to mean a molecular includant having more than two leaving groups covalently coupled to each molecule of molecular includant. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of molecular includants include, but are not limited to, the cyclodextrins.

The term "artificial light" is used herein to mean light having a relatively broad bandwidth that is produced from conventional light sources, including, but not limited to, conventional incandescent light bulbs and fluorescent light bulbs.

The term "thereon" is used herein to mean thereon or therein. For example, the present invention includes a substrate having a colored composition thereon. According to the definition of "thereon" the colored composition may be present on the substrate or it may be in the substrate.

Admixing Stabilizing Molecules Into Colorant Solutions.

The present invention relates to colorant compositions having improved stability, wherein the colorant stabilizer is associated with a colorant solution. Desirably, the colorant stabilizer is admixed with a colorant solution. The colorant stabilizer is desirably one or more porphines alone or in combination with at least one metal or metal salt. The colorant stabilizers of the present invention are admixed with a colorant to stabilize the colorant when the admixture is exposed to electromagnetic radiation such as artificial light or sunlight.

The present invention further relates to a method of stabilizing a colorant comprising associating one or more of the colorant stabilizers with the colorant solution. Optionally, the colorant stabilizer may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the colorant stabilizer and the colorant.

The present invention is particularly useful for stabilizing inks to be used in ink jet printers. Inks used in ink jet printers are described in U.S. patent application Ser. No. 08/769,885 filed on Dec. 19, 1996, which is a continuation of U.S. patent application Ser. No. 08/461,382 filed on Jun. 5, 1995, now abandoned, which is a divisional of U.S. patent application Ser. No. 08/461,365 filed on Jun. 5, 1995, now abandoned, all of which are incorporated herein by reference.

In another embodiment of the present invention, a colorant stabilizer is represented by porphines having an extremely short triplet state lifetime. (See e.g., Kubat, et al., Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) porphyrin, J. Photochem. and Photbio. A: Chemistry 96 (1996), pgs 93-97 which is incorporated herein by reference). Particularly suitable porphines include, but are not limited to, porphines having the following structure: ##STR4## wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO₃ H, ##STR5## COOH, or R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.

Desirably, the colorant stabilizer is represented by the porphines Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine (designated CuTMPS4), having the following structure: ##STR6## The copper ion can also be substituted with an iron or cobalt ion. It is also understood that in the case of FeTPPS4, CuTPPS4 or CoTPPS4, the sulfuric acid moieties may be substituted with salts when in solution, such as sodium salts. The colorant solution may be stabilized with about 0.1% to 10% wt/wt porphine, more preferably about 0.3% to 1% wt/wt porphine, and more preferably about 0.5% wt/wt porphine.

In another embodiment, the colorant stabilizer comprises one or more porphines in combination with one or more metals or metal salts, such as lanthanides and lanthanide salts. Desirably, the amount of metal or metal salt in the colorant solution is from about 0.01% to 10% wt/wt metal, more desirably about 0.03% to 1% wt/wt metal, and more desirably about 0.05% wt/wt metal. Although lanthanides and lanthanide salts are desired metals, other metals, may also be used such as magnesium, iron, zinc, and other transition metals. To improve the solubility of the metal or metal salt in solution, metal solubility-enhancing agents may be added. Particularly useful metal solubility-enhancing agents include, but are not limited to, chelating agents, including, but not limited to, EDTA (ethylenediaminetetraacetic acid) or EGTA (ethylene glycol-bis(β-aminoethyl ether)).

In a further embodiment, the colorant stabilizer comprises a porphine and a lanthanide, such as europium. Desirably, the amount of porphine in the colorant solution is from about 0.1% to 10% wt/wt porphine, more desirably about 0.3% to 1% wt/wt porphine, and more desirably about 0.5% wt/wt porphine. Desirably, the amount of lanthanide in the colorant solution is from about 0.01% to 10% wt/wt lanthanide, more desirably about 0.03% to 1% wt/wt lanthanide, and more desirably about 0.05% wt/wt lanthanide. Although europium and europium salts are desired lanthanides, other lanthanides, may also be used.

Although not wanting to be limited by the following, it is theorized that the above stabilizing compounds of the present invention, either admixed with a colorant solution or on or in a substrate to which the colorant is applied, act by quenching the excited state of a dye molecule by efficiently returning it to a ground state. This reduces the likelihood of an oxidative or other chemical reaction occurring which would render the dye chromophore colorless.

The quenching process can occur by a number of processes. One such process is referred to as the heavy atom effect (internal or external) in which atoms with a high atomic number, such as iodine, xenon and lanthanides, can effect the excited electronic transitions of the dye molecule by allowing here to fore forbidden electronic transitions to occur and by decreasing the excited state lifetimes. This effect permits the rapid return of the dye to its ground state.

Another quenching process involves back electron transfer. In this case, quenching of the excited dye molecule occurs through sequential electron transfer. The additive or quencher, and dye form an ion pair through electron donation within which back electron transfer leads to an overall deactivation of the excited energy donor, i.e., the dye.

Another quenching process involves a condition in which the quencher (additive) molecule has an excited energy state lower than the excited dye. In this case, it may be possible to transfer the excited energy to the quencher thereby allowing the dye molecule to return to its ground state. These mechanisms are more fully discussed in Chemistry and Light, Suppan, P., Published by The Royal Society of Chemistry, 1994, pgs 65-69 which is incorporated herein by reference.

The dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-α- 4-(dimethylamino)phenyl!-α-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4- 4-(dimethylamino)phenyl!phenyl-methylene!-2,5-cyclohexyldien-1-ylidene!-N-methyl-methanaminium chloride or bis p-(dimethylamino)phenyl!phenylmethylium chloride }, and Malachite Green oxalate {N-4- 4-(dimethylamino)-phenyl!-phenylmethylene!-2,5-cyclohexyldien-1-ylidene!-N-methyl-methanaminium chloride or bis p-(dimethylamino)-phenyl!phenylmethyliurn oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride!, Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and β-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt 3,7-bis(dimethylamino)-6-nitrophenothiazin-5-ium chloride, zinc chloride double salt!; oxazine dyes, such as Lumichrome (7,8-dimethylalloxazine); naphthalimide dyes, such as Lucifer Yellow CH {6-amino-2- (hydrazinocarbonyl)amino!-2,3-dihydro-1,3-dioxo-1H-benz de!iso-quinoline-5,8-disulfonic acid dilithium salt}; azine dyes, such as Janus Green B {3-(diethylamino)-7- 4-(dimethylamino)phenyl!azo!-5-phenylphenazinium chloride}; cyanine dyes, such as Indocyanine Green {Cardio-Green or Fox Green; 2- 7- 1,3-dihydro-1,1-dimethyl-3-(4-sulfobutyl)-2H-benz e!indol-2-ylidene!-1,3,5-heptatrienyl!-1,1-dimethyl-3-(4-sulfobutyl)-1H-benz e!indolium hydroxide inner salt sodium salt}; indigo dyes, such as Indigo {Indigo Blue or Vat Blue 1; 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihydro-3H-indol-3-one}; coumarin dyes, such as 7-hydroxy-4-methyl-coumarin (4-methylumbelliferone); benzimidazole dyes, such as Hoechst 33258 bisbenzimide or 2-(4-hydroxyphenyl)-5-(4-methyl-1-piperazinyl)-2,5-bi-1H-benzimidazole trihydrochloride pentahydrate!; paraquinoidal dyes, such as Hematoxylin {Natural Black 1; 7,11b-dihydrobenz b!-indeno 1,2-d!pyran-3,4,6a,9,10(6H)-pentol)}; fluorescein dyes, such as Fluoresceinamine (5-aminofluorescein); diazonium salt dyes, such as Diazo Red RC (Azoic Diazo No. 10 or Fast Red RC salt; 2-methoxy-5-chlorobenzenediazonium chloride, zinc chloride double salt); azoic diazo dyes, such as Fast Blue BB salt (Azoic Diazo No. 20; 4-benzoylamino-2,5-diethoxy-benzene diazonium chloride, zinc chloride double salt); phenylenediamine dyes, such as Disperse Yellow 9 N-(2,4-dinitrophenyl)-1,4-phenylenediamine or Solvent Orange 53!; diazo dyes, such as Disperse Orange 13 Solvent Orange 52; 1-phenylazo-4-(4-hydroxyphenylazo)naphthalene!; anthraquinone dyes, such as Disperse Blue 3 Celliton Fast Blue FFR; 1-methylamino-4-(2-hydroxyethylamino)-9,10-anthraquinone!, Disperse Blue 14 Celliton Fast Blue B; 1,4-bis(methylamino)-9,10-anthraquinone!, and Alizarin Blue Black B (Mordant Black 13); trisazo dyes, such as Direct Blue 71 {Benzo Light Blue FFL or Sirius Light Blue BRR; 3- (4- (4- (6-amino-1-hydroxy-3-sulfo-2-naphthalenyl)azo!-6-sulfo-1-naphthalenyl)-azo!-1-naphthalenyl)azo!-1,5-naphthalenedisulfonic acid tetrasodium salt}; xanthene dyes, such as 2,7-dichlorofluorescein; proflavine dyes, such as 3,6-diaminoacridine hemisulfate (Proflavine); sulfonaphthalein dyes, such as Cresol Red (o-cresolsulfonaphthalein); phthalocyanine dyes, such as Copper Phthalocyanine {Pigment Blue 15; (SP-4-1)- 29H,31H-phthalocyanato(2-)-N²⁹,N³⁰,N³¹,N³² !copper}; carotenoid dyes, such as trans-β-carotene (Food Orange 5); carminic acid dyes, such as Carmine, the aluminum or calcium-aluminum lake of carminic acid (7-a-D-glucopyranosyl-9,10-dihydro-3,5,6,8-tetrahydroxy-1-methyl-9,10-dioxo-2-anthracenecarbonylic acid); azure dyes, such as Azure A 3-amino-7-(dimethylamino)phenothiazin-5-ium chloride or 7-(dimethylamino)-3-imino-3H-phenothiazine hydrochloride!; and acridine dyes, such as Acridine Orange Basic Orange 14; 3,8-bis(dimethylamino)acridine hydrochloride, zinc chloride double salt! and Acriflavine (Acriflavine neutral; 3,6-diamino-10-methylacridinium chloride mixture with 3,6-acridine-diamine).

In some embodiments of the present invention, the colorant and/or colorant stabilizer is associated with a molecular includant. The term "associated" in its broadest sense means that the colorant and/or colorant stabilizer is at least in close proximity to the molecular includant. For example, the colorant and/or colorant stabilizer may be maintained in close proximity to the molecular includant by hydrogen bonding, van der Waals forces, or the like. Alternatively, the colorant and/or colorant stabilizer may be covalently bonded to the molecular includant, although this normally is neither desired nor necessary. As a further example, the colorant and/or colorant stabilizer may be at least partially included within the cavity of the molecular includant.

The molecular includant can be added to the colorant solution or incorporated into a substrate, such as paper, which is subsequently coated with the colorant solution. The molecular includant can be inorganic or organic in nature. In certain embodiments, the chemical structure of the molecular includant is adapted to form a molecular inclusion complex. Examples of molecular includants are, by way of illustration only, clathrates or intercalates, zeolites, and cyclodextrins. Examples of cyclodextrins include, but are not limited to, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β cyclodextrin and sulfated γ-cyclodextrin (Cerestar U.S.A., Incorporated, Hammond, Ind.).

The term "derivatized cyclodextrin" as used herein means a cyclodextrin having more than two leaving groups covalently coupled to each molecule of cyclodextrin. The term "leaving group" is used herein to mean any leaving group capable of participating in a bimolecular nucleophilic substitution reaction. Examples of derivatized cyclodextrin includes, but is not limited to, hydroxypropyl β-cyclodextrin, hydroxyethyl β-cyclodextrin, hydroxyethyl α cyclodextrin, carboxymethyl α cyclodextrin, carboxymethyl β cyclodextrin, carboxymethyl γ cyclodextrin, octyl succinated α cyclodextrin, octyl succinated β cyclodextrin, octyl succinated γ cyclodextrin and sulfated β and γ-cyclodextrin. A desired derivatized cyclodextrin is ethylhydroxy β-cyclodextrin.

A desired molecular includant is γ-cyclodextrin. Another desirable molecular includant is β-cyclodextrin. In other embodiments, the molecular includant is an ethyl hydroxy β-cyclodextrin. Although not wanting to be bound by the following theory, it is believed that the molecular includant inhibits the aggregation of the colorant molecule in solution. Other aggregation inhibitors that can be used in practicing the present invention are starches, pectins, amyloses, clathrates and the crown ethers. It is to be understood that the addition of derivatized cyclodextrins to an ink formulation for the purpose of inhibiting aggregation and/or stabilizing the dyes in the inks is considered one aspect of the present invention.

As a practical matter, the colorant, the colorant stabilizer and molecular includant are likely to be solids depending upon the constituents used to prepare the molecules. However, any or all of such materials can be a liquid. The colored composition can be a liquid either because one or more of its components is a liquid, or, when the molecular includant is organic in nature, a solvent is employed. Suitable solvents include, but are not limited to, amides, such as N,N-dimethylformamide; sulfoxides, such as dimethylsulfoxide; ketones, such as acetone, methyl ethyl ketone, and methyl butyl ketone; aliphatic and aromatic hydrocarbons, such as hexane, octane, benzene, toluene, and the xylenes; esters, such as ethyl acetate; water; and the like. When the molecular includant is a cyclodextrin, particularly suitable solvents are the amides and sulfoxides.

In an embodiment where the composition of the present invention is a solid, the effectiveness of the above compounds on the colorant is improved when the colorant and the selected compounds are in intimate contact or in an association that approaches van der Waals radii. To this end, the thorough blending of the components, along with other components which may be present, is desirable. Such blending generally is accomplished by any of the means known to those having ordinary skill in the art. When the colored composition includes a polymer, blending is facilitated if the colorant and the colorant stabilizer are at least partly soluble in softened or molten polymer. In such case, the composition is readily prepared in, for example, a two-roll mill. Alternatively, the composition of the present invention can be a liquid because one or more of its components is a liquid.

For some applications, the composition of the present invention typically will be utilized in particulate form. In other applications, the particles of the composition should be very small. Methods of forming such particles are well known to those having ordinary skill in the art.

The colored composition optionally may also contain a carrier, the nature of which is well known to those having ordinary skill in the art. For many applications, the carrier will be a polymer, typically a thermosetting or thermoplastic polymer, with the latter being the more common. Examples of suitable thermosetting and thermoplastic polymers are disclosed in parent U.S. patent application Ser. No. 08/843,410, assigned to Kimberly Clark Worldwide, Inc., the entire content of which is hereby incorporated by reference.

In addition to the colorant, colorant stabilizer, and optional molecular includant, the colored composition of the present invention also can contain additional components, depending upon the application for which it is intended. Examples of such additional components include, but are not limited to, charge carriers; stabilizers against thermal oxidation; viscoelastic properties modifiers; cross-linking agents; plasticizers; charge control additives such as a quaternary ammonium salt; flow control additives such as hydrophobic silica, zinc stearate, calcium stearate, lithium stearate, polyvinylstearate, and polyethylene powders; fillers such as calcium carbonate, clay and talc; surfactants; chelating agents; and TINUVIN® compounds; among other additives used by those having ordinary skill in the art. Charge carriers are well known to those having ordinary skill in the art and typically are polymer-coated metal particles. Desirable surfactants include , but are not limited to, C₁₂ to C₁₈ surfactants such as cetyl trimethyl ammonium chloride and carboxymethylamylose. TINUVIN® compounds are a class of compounds produced by Ciba-Geigy Corporation, which includes benzophenones, benzotriazoles and hindered amines. Desirable TINUVIN® compounds include, but are not limited to, 2-(2'-hydroxy-3'-sec-butyl-5'-tert-butylphenyl)-benzotriazole, poly-(N-β-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate and 2-(2'-hydroxy-3',5'-ditert butylphenyl)-5-chloro-benzotriazole. The identities and amounts of such additional components in the colored composition are well known to one of ordinary skill in the art.

When the colorant stabilizers of the present invention are used to stabilize the dyes in ink jet inks, it is desirable to filter the compositions through a small pore filter (0.45μ) such as a Millipore® filter before the ink formulation is placed in an ink jet cartridge. This will reduce or eliminate clogging of the cartridge ink nozzles due to particulate matter.

The colorant stabilizers of the present invention enable the formation of ink sets comprising one or more inks, wherein each ink of the ink set, regardless of color, possesses similar light fastness properties as the other inks in the ink set. Such ink sets may be used to produce multi-color text and/or graphics, which uniformly retain their color over extended periods of time and/or upon extended exposure to light. One desirable ink set includes cyan, magenta, yellow and black inks, wherein the magenta ink contains colorant stabilizers in the form of a porphine and a metal, such as europium, and the yellow ink contains a colorant stabilizer in the form of a porphine without the metal. Another desirable ink set includes cyan, magenta, yellow and black inks, wherein the cyan ink contains a colorant stabilizer in the form of a benzophenone, and the magenta and yellow inks contain colorant stabilizers in the form of a porphine and a metal, such as europium.

It is to be understood that in any desired ink set, a single ink may be stabilized according to the present invention or several of the inks may be stabilized utilizing one or more of the stabilizing agents described herein. Other ink sets are within the scope of the present invention. Included in the present invention are ink sets wherein the black color is a pigment and the other colors in the ink set are dyes. Although ink sets wherein the inks possess substantially identical light fastness properties are desirable, in some embodiments, it may be desirable to produce ink sets wherein the inks within the ink set have specifically controlled, varying light fastness properties.

The substrates to which the colorant and colorant stabilizers are applied include, but are not limited to, paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, metal, or any other substrate that would benefit from having a stabilized colorant thereon. Examples of suitable substrates are disclosed in parent U.S. patent application Ser. No. 08/843,410, assigned to Kimberly Clark Worldwide, Inc., the entire content of which is hereby incorporated by reference.

The present invention is further described by the examples which follow. Such examples, however, are not to be construed as limiting in any way either the spirit or scope of the present invention. In the examples, all parts are parts by weight unless stated otherwise.

EXAMPLE 1 Preparation and Testing of Inks Containing Porphine Colorant Stabilizers

This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on treated or untreated paper. More particularly, the paper is untreated Hewlett-Packard premium paper, or treated Hewlett-Packard premium paper prepared using a solution of about 50% wt/wt hydroxypropyl γ-cyclodextrin to ink, in or on the paper in a concentration of about 5 to 15% wt/wt solution to paper.

The stabilizing additives of this example are porphines. Specifically, the porphines Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) and Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine (designated CuTMPS4) (available from Porphyrin Products, Inc., Logan, Utah) were used, which are represented by the following structures, respectively: ##STR7##

The invention provides that the metal ion Co or Cu may be used interchangeably in the porphine structures of the present invention. Additional background on the chemistry of porphines can be found in Kubat et al. "Photophysical properties of metal complexes of meso-tetrakis (4-sulphonatophenyl) Porphyrin," Journal of Photochemistry and Photobiology A:Chemistry 96 (1996) 93-97, and references cited therein, hereby incorporated by reference.

Printed sheets of paper were placed in the Atlas weatherometer and exposed for the designated number of hours under the following conditions: 0.54 W/m² at 440 nm, 55% humidity, 45° C. black panel temperature, borosilicate filters.

The change in magenta color is measured by the Xrite Colorimeter (Model 938, SpectroDensitometer, Grandville, Mich.) which measures the ΔE* values, based on the L, a*, b* as described by Cielab, D-50-2. The results are reported in the tables below.

The treated and untreated paper is printed with inks designated A1, A2, A3, A4, B1, B2, B3, B4, C1, C2, C3, and C4, prepared as follows:

    ______________________________________     A1 Ink       DI Water    84.80%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              4.00                  Acid Red 52 0.40     A2 Ink       DI Water    85.40%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              3.00                  Acid Red 52 0.80     A3 Ink       DI Water    86.00%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              2.00                  Acid Red 52 1.20     A4 Ink       DI Water    86.60%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              1.00                  Acid Red 52 1.60     B1 Ink       DI Water    83.02%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              5.78                  Acid Red 52 0.40     B2 Ink       DI Water    84.07%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              4.33                  Acid Red 52 0.80     B3 Ink       DI Water    85.11%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              2.89                  Acid Red 52 1.20     B4 Ink       DI Water    86.16%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              1.44                  Acid Red 52 1.60     C1 Ink       DI Water    82.62%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              6.18                  Acid Red 52 0.40     C2 Ink       DI Water    82.62%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              4.63                  Acid Red 52 0.80     C3 Ink       DI Water    84.91%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              3.09                  Acid Red 52 1.20     C4 Ink       DI Water    86.06%                  2 Pyrrolidone                              10.00                  Giv Guard DXN                              00.20                  Cobratec 99 00.10                  Triethanolamine                              00.50                  Reactive Red 120                              1.54                  Acid Red 52 1.60     ______________________________________

The above inks were fade tested with the following results.

    ______________________________________     Inks Without Additives                      63H     Ink ID#          ΔE*                             ΔH*     ______________________________________     A1               47.8   7.5     A2               57.5   21.6     A3               60.7   33.8     A4               62.1   43.2     B1               38     -0.54     B2               46.4   14.8     B3               56.3   28.4     B4               64.7   39.1     C1               69.4   2.6     C2               64.3   11.3     C3               72.4   20.5     C4               83.9   22.7     ______________________________________

The inks were prepared with about 0.5% CuTPPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

    ______________________________________     Inks made with 0.5% CuTPPS.sub.4 on HP premium paper     Samples  15H             78H         94H     ID#      ΔE*                     ΔH*                              ΔE*                                   ΔH*                                          ΔE*                                               ΔH*     ______________________________________     A1       9.6    4.8      34.7 12.1   41.6 12.8     A2       14.7   12.8     41.8 23.8   48.8 24.9     A3       19.6   18.7     42.7 31.9   47   32.7     A4       29.6   28.9     51.8 42.4   55.5 42.1     B1       8.2    1.8      30.6 8.8    38.2 9.2     B2       8.3    6.3      32.3 17.8   37.8 18.8     B3       14.9   13.8     39.0 27.5   44.5 28.6     B4       25.2   24.6     47.7 38.3   51.6 38.5     C1       14.3   -7.71    41.8 8.9    N/A  N/A     C2       7.9    -2.7     33.7 13.9   N/A  N/A     C3       9.2    6.9      37.9 23.6   N/A  N/A     C4       23.1   22.2     48.6 37.7   N/A  N/A     ______________________________________

    ______________________________________     Inks with 0.5% CuTPPS.sub.4 on Hydroxy-Propyl γ-CD paper     Samples  15H             78H         94H     ID#      ΔE*                     ΔH*                              ΔE*                                   ΔH*                                          ΔE*                                               ΔH*     ______________________________________     A1       1.5    -0.2     6.6  -3.2   8    -4.1     A2       1.2    0.28     4.1  -0.8   5.4  -1.3     A3       2.8    2.14     5    4.3    5.2  4.3     A4       4.9    4.7      10.4 9.8    10.2 9.5     B1       3.1    -1.5     9.4  -5.5   11.2 -6.9     B2       2.3    -2.4     7.7  -5.2   8.3  -5.7     B3       1.2    1.1      4.1  0.13   4.7  -0.79     B4       2.9    2.6      7.2  6.3    7.7  6.5     C1       4      -3.3     17.1 -13.8  N/A  N/A     C2       3      -2.6     3.4  -2.8   N/A  N/A     C3       1.6    -1.5     5.2  -3.3   N/A  N/A     C4       1.4    1.1      4.7  3.5    N/A  N/A     ______________________________________

Additionally, HP-1600 magenta ink was prepared with about 0.5% CuTPPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

    ______________________________________     15 Hour Multiple Samples     Samples ID#      ΔE*                             ΔH*     ______________________________________     HP #1            14.68  13.13     HP #2            20.86  19.50     HP #3            17.01  15.55     HP #4            13.04  11.15     HP #5            13.11  10.57     HP #6            13.09  11.10     HP γ-CD #1 2.66   -1.47     HP γ-CD #2 1.20   -.53     HP γ-CD #3 2.44   -.53     HP γ-CD #4 1.30   -.47     HP γ-CD #5 1.74   -.30     HP γ-CD #6 1.35   -.34     ______________________________________

The HP-1600 magenta ink was also prepared with about 0.5% CuTMPS₄ stabilizing additive and fade tested on HP paper and HP γ-CD paper with the following results.

    ______________________________________     15 Hour Multiple Samples     ______________________________________     HP #1            13.94  11.39     HP #2            13.58  11.11     HP #3            13.98  11.57     HP #4            14.16  11.56     HP γ-CD #1 2.32   -.99     HP γ-CD #2 1.44   -1.05     HP γ-CD #3 2.17   -.67     HP γ-CD #4 1.98   -1.21     HP γ-CD #5 2.14   -1.38     HP γ-CD #6 1.79   -.85     HP γ-CD #7 .36    .15     ______________________________________

EXAMPLE 2 Preparation and Testing of Inks Containing Porphine and Lanthanide Colorant Stabilizers

This example reports the results of fade testing of various inks, either with or without the stabilizing additives of the present invention, on untreated paper. More particularly, the paper is untreated QIS Photo Glossy paper.

The stabilizing additives of this example are porphines and europium salts. Specifically, the porphine Cu-meso-tetra-(4-sulfanatophenyl)-porphine (designated CuTPPS4) (available from Porphyrin Products, Inc., Logan, Utah) is used, as in Example 1 above. The europium salt, europium nitrate (designated EuN) (Strem Chemical Co., Newburyport, Mass.) is used.

A forty-eight hour accelerated fade test of various magenta ink composition was performed. A magenta control without stabilizing additives was applied to the QIS paper medium. After subjecting the ink composition and paper medium to the forty-eight hour test, ΔE* and ΔH* values were measured. Similar measurements were taken using the following ink formulations:

a) magenta+0.5 wt % CuTPPS4

b) magenta+0.05 wt % EuN

c) magenta+0.5 wt % CuTPPS4+0.05 wt % EuN.

The resulting measurements are given below.

    ______________________________________     Ink Formulation                    Media         ΔE*                                         ΔH*     ______________________________________     Magenta Control                    QIS Photo Glossy                                  31.8   24.5     Magenta + CuTPPS4                    QIS Photo Glossy                                  16.4   -3.7     Magenta + EuN  QIS Photo Glossy                                  19.6   17.3     Magenta + CuTPPS4 +                    QIS Photo Glossy                                  7.8    2.8     EuN     ______________________________________

Having thus described the invention, numerous changes and modifications thereof will be readily apparent to those having ordinary skill in the art, without departing from the spirit or scope of the invention. 

What is claimed is:
 1. An ink set comprising two or more inks, wherein one or more inks of the ink set contain a porphine.
 2. The ink set of claim 1, wherein the porphine is represented by the following formula ##STR8## wherein M is iron, cobalt or copper; and wherein R is SO₃ H, ##STR9## COOH, or R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.
 3. The ink set of claim 2, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR10## or the porphine is Co-meso-tetra-(4-sulfanatophenyl)-porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR11##
 4. The ink set of claim 1, wherein a metal or metal salt is added to the one or more inks containing the porphine.
 5. The ink set of claim 4, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.
 6. The ink set of claim 5, wherein the lanthanide or lanthanide salt comprises an europium or europium salt.
 7. The ink set of claim 1, wherein the porphine is associated with a molecular includant.
 8. The ink set of claim 7, wherein the molecular includant is one or more cyclodextrins.
 9. The ink set of claim 8, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.
 10. A composition comprising a colorant and at least one porphine.
 11. The composition of claim 10, wherein at least one porphine is represented by the following formula ##STR12## wherein M is iron, cobalt or copper; and wherein R is SO₃ H, ##STR13## COOH, or R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.
 12. The composition of claim 11, wherein at least one porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR14## or the porphine is Co-meso-tetra-(4-sulfanatophenyl)-porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR15##
 13. The composition of claim 12, further comprising a metal or a metal salt.
 14. The composition of claim 13, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.
 15. The composition of claim 14, wherein the lanthanide or lanthanide salt comprises europium or europium salt.
 16. The composition of claim 10, wherein the at least one porphine is associated with a molecular includant.
 17. The composition of claim 16, wherein the molecular includant is one or more cyclodextrins.
 18. The composition of claim 17, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.
 19. A method of stabilizing a colorant comprising associating at least one porphine with the colorant.
 20. The method of claim 19, wherein at least one porphine is represented by the following formula ##STR16## wherein M is iron, cobalt or copper; and wherein R is SO₃ H, ##STR17## COOH, or R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.
 21. The method of claim 19, further comprising associating a metal or metal salt with the colorant.
 22. The method of claim 21, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.
 23. The method of claim 22, wherein the lanthanide or lanthanide salt comprises europium or europium salt.
 24. The method of claim 19, wherein the at least one porphine is associated with a molecular includant.
 25. The method of claim 24, wherein the molecular includant is one or more cyclodextrins.
 26. The composition of claim 25, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.
 27. The method of claim 19, further comprising:associating a colorant stabilizer with a second colorant; and forming an ink set of the colorants.
 28. A colorant stabilizing composition comprising a porphine.
 29. The colorant stabilizing composition of claim 28, wherein the porphine is represented by the following formula ##STR18## wherein M is iron, cobalt or copper; and wherein R is SO₃ H, ##STR19## R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.
 30. The colorant stabilizing composition of claim 29, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR20## or the porphine is Co-meso-tetra-(4-sulfanatophenyl)-porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR21##
 31. The colorant stabilizing composition of claim 28, further comprising a metal or a metal salt.
 32. The colorant stabilizing composition of claim 31, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.
 33. The colorant stabilizing composition of claim 32, wherein the lanthanide or lanthanide salt comprises europium or europium salt.
 34. The colorant stabilizing composition of claim 31, wherein the metal or metal salt comprises magnesium, iron, zinc, or other transition metals or their salts.
 35. The colorant stabilizing composition of claim 28, further comprising a molecular includant.
 36. The colorant stabilizing composition of claim 35, wherein the molecular includant is one or more cyclodextrins.
 37. The colorant stabilizing composition of claim 36, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, g-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.
 38. The colorant stabilizing composition of claim 28, further comprising a colorant.
 39. The colorant stabilizing composition of claim 28, further comprising a carrier.
 40. The colorant stabilizing composition of claim 39, wherein the carrier is a thermosetting or thermoplastic polymer.
 41. A substrate having thereon or therein the colorant stabilizing composition of claim
 28. 42. A substrate having thereon or therein a colorant stabilizing composition comprising a porphine.
 43. The substrate of claim 42, wherein the substrate comprises paper, wood, a wood product or composite, woven fabric, nonwoven fabric, textile, plastic, glass, or any combination thereof.
 44. The substrate of claim 42, wherein the porphine is represented by the following formula ##STR22## wherein M is iron, cobalt or copper; and wherein R is SO₃ H, ##STR23## R₁ COOH wherein R₁ is an alkyl group of from 1 to 6 carbons.
 45. The substrate of claim 44, wherein the porphine is Cu-meso-tetra-(4-sulfanatophenyl)-porphine or Cu-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR24## or the porphine is Co-meso-tetra-(4-sulfanatophenyl)-porphine or Co-meso-tetra-(N-methyl-4-pyridyl)-porphine, having the following structures, respectively: ##STR25##
 46. The substrate of claim 42, further comprising a metal or a metal salt associated with the porphine.
 47. The substrate of claim 46, wherein the metal or metal salt comprises a lanthanide or lanthanide salt.
 48. The substrate of claim 47, wherein the lanthanide or lanthanide salt comprises europium or europium salt.
 49. The substrate of claim 46, wherein the metal or metal salt comprises magnesium, iron, zinc, or other transition metals or their salts.
 50. The substrate of claim 42, further comprising a molecular includant associated with the porphine.
 51. The substrate of claim 50, wherein the molecular includant is one or more cyclodextrins.
 52. The substrate of claim 51, wherein the one or more cyclodextrins comprise α-cyclodextrin, β-cyclodextrin, g-cyclodextrin, δ-cyclodextrin, hydroxypropyl β-cyclodextrin, or hydroxyethyl β-cyclodextrin.
 53. The substrate of claim 42, further comprising a colorant thereon. 